Chelating base product for use in water-based system treatments

ABSTRACT

A base product fluid is produced by adding anhydrous liquid ammonia and a first portion of sulfuric acid to water in a process line to form a mixed fluid. The mixed fluid may be cooled and a second portion of sulfuric acid may be added to the mixed fluid to form the base product fluid. The base product fluid may include a molecular compound that is a chelating compound. The molecular compound may have the formula: ((NH 4 ) 2 SO 4 ) a .(H 2 SO 4 ) b .(H 2 O) c .(NH 4 HSO 4 ) x . In the formula, a may be between 1 and 5, b may be between 1 and 5, c may be between 0 and 5, and x may be between 1 and 20.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a divisional of U.S. patent application Ser. No.16/046,387, filed on Jul. 26, 2018, which is a continuation of U.S.patent application Ser. No. 15/388,767, filed on Dec. 22, 2016 (nowissued U.S. Pat. No. 10,093,564), which is a continuation-in-part ofU.S. patent application Ser. No. 15/184,523, filed on Jun. 16, 2016 (nowissued U.S. Pat. No. 9,938,171), which claims priority to U.S.Provisional Patent Application No. 62/182,191, filed on Jun. 19, 2015,the entire contents of each of which are incorporated by referenceherein.

BACKGROUND 1. Field of the Invention

The present invention relates to a base product used for variouswater-based treatment systems. More particularly, the invention relatesto a base product fluid with a chelating compound having a selectedformula, methods for making the based product fluid with the chelatingcompound, and applications for an end product formed from the basedproduct fluid.

2. Description of Related Art

Base products such as chelating agents have been blended with coppersulfate for various uses in water-based treatment systems. U.S. Pat. No.4,564,504 to Sorber, which is incorporated by reference as if fully setforth herein, discloses an early process (the “Sorber process”) thatused water, ammonia, and sulfuric acid to produce a novel acid. TheSorber process involved a vat mixing batch process where sulfuric acidis slowly mixed to an aqueous ammonium solution. The Sorber process wasperformed in open vats and was dangerous due to the extremely exothermicnature of the reactions involved. The Sorber process may be termed a“cold process” as the mixing was slowed down to avoid excess heatgeneration and/or explosions from occurring.

There have been several attempts to improve upon the “cold process”(Sorber process). Examples of these attempts are found in U.S. Pat. No.5,989,595 to Cummins, U.S. Pat. No. 6,242,011 to Cummins, U.S. Pat. No.RE41,109 to Cummins, and U.S. Pat. No. 8,012,511 to Cummins, each ofwhich is incorporated by reference as if fully set forth herein. Inaddition, a vat mixing process involving the use of high pressure andhigh voltage DC current was attempted.

SUMMARY

In certain embodiments, a chelating compound has the formula:((NH₄)₂SO₄)_(a).(H₂SO₄)_(b).(H₂O)_(c).(NH₄HSO₄)_(x); where a is between1 and 5, b is between 1 and 5, c is between 0 and 5, and x is between 1and 20. In certain embodiments, a chelating compound has the formula:((NH₄)₂SO₄)_(a).(H₂SO₄)_(b).(H₂O)_(c).(NH₄HSO₄)_(x); where a is at least1, b is at least 1, c is at least 0, and x is between 1 and 20. In someembodiments, the chelating compound includes an elemental compositionof: between about 3% and about 6% hydrogen; between about 10% and about15% nitrogen; between about 25% and about 30% sulfur; and between about52% and about 60% oxygen. In some embodiments, the chelating compoundhas a pH below about 2 when mixed with water.

In certain embodiments, a chelating compound is formed by a processincluding combining a molecular compound with sulfuric acid and water.The molecular compound may have the formula:((NH₄)₂SO₄)_(a).(H₂SO₄)_(b).(H₂O)_(c).(NH₄HSO₄)_(x); where a is between1 and 5, b is between 1 and 5, c is between 0 and 5, and x is between 1and 20. In some embodiments, the molecular compound is formed by aprocess of flowing water through a process line; adding and mixinganhydrous liquid ammonia and a first portion of sulfuric acid to waterin a process line to form a mixed fluid; and cooling the mixed fluid byflowing the mixed fluid through a heat exchanger to form an intermediatefluid with the molecular compound.

In certain embodiments, a chelating compound is formed by a processincluding combining a molecular compound with an acid and water. Themolecular compound may have the formula:((NH₄)₂SO₄)_(a).(H₂SO₄)_(b).(H₂O)_(c).(NH₄HSO₄)_(x); where a is between1 and 5, b is between 1 and 5, c is between 0 and 5, and x is between 1and 20. In certain embodiments, a chelating compound is formed by amethod that includes adding and mixing anhydrous liquid ammonia and afirst portion of an acid to flowing water in a process line to form amixed fluid; cooling the mixed fluid by flowing the mixed fluid througha heat exchanger; and adding a second portion of the acid to the mixedfluid to form a product fluid comprising the chelating compound, whereinthe second portion of the acid is greater than the first portion of theacid. The acid may be phosphoric acid (or a derivative of phosphoricacid), a hydrogen halide, nitric acid, and/or sulfuric acid.

BRIEF DESCRIPTION OF THE DRAWINGS

Features and advantages of the methods and apparatus of the presentinvention will be more fully appreciated by reference to the followingdetailed description of presently preferred but nonetheless illustrativeembodiments in accordance with the present invention when taken inconjunction with the accompanying drawings in which:

FIG. 1 depicts a representation of an embodiment of a process system forproducing an embodiment of a base product fluid.

FIG. 2 depicts a detailed representation of an embodiment of a firstsubsystem.

FIG. 3 depicts a detailed representation of an embodiment of a secondsubsystem.

FIG. 4 depicts a detailed representation of an embodiment of a thirdsubsystem.

FIG. 5 depicts a detailed representation of an embodiment of a fourthsubsystem.

FIG. 6 depicts a detailed representation of an embodiment of a fifthsubsystem.

FIG. 7 depicts an example of an embodiment of a water tank.

FIG. 8 depicts an example of an embodiment of an anhydrous liquidammonia cylinder.

FIG. 9 depicts an example of an embodiment of an acid tank.

FIG. 10 depicts an example of another embodiment of an acid tank.

FIG. 11 depicts an example of an embodiment of a start-up tank.

FIGS. 12A-F depicts various mixer configurations of orifice mixers andstatic mixers.

FIG. 13 depicts a 210 nm chromatogram of the base product fluid usingSE-HPLC.

FIG. 14 depicts a plot of infrared (IR) spectra comparing the baseproduct to ammonium bisulfate ((NH₄)HSO₄).

FIG. 15 depicts plots of X-ray diffraction analysis (XRD) spectracomparing the base product to ammonium bisulfate ((NH₄)HSO₄) andammonium sulfate ((NH₄)₂SO₄).

FIG. 16 depicts time-of-flight mass spectrometry (TOFMS) of the baseproduct fluid.

FIG. 17 depicts a high-resolution mass spectrum of the base productfluid for masses 100-800.

FIG. 18 depicts a high-resolution mass spectrum of the base productfluid for masses 700-1600.

FIG. 19 depicts a side-view representation of a copper diffusion testingapparatus.

FIG. 20 depicts a cross-section end view of a pipe with water in thepipe.

FIG. 21 depicts plots of copper concentration versus time at the 30 cmsampling location for the chelated copper described herein, designatedESL-Cu, and copper sulfate, designated CuSO₄.

FIG. 22 depicts surface diffusion profiles of ESL-Cu and CuSO₄ after a72-hour hold-time.

FIG. 23 depicts the bottom concentration diffusion profiles of ESL-Cuand CuSO₄ after a 72-hour hold-time.

FIG. 24 depicts inhibition concentrations for 25 percent reduction(IC₂₅) and 50 percent reduction (IC₅₀) in reproduction or growth usingthe end product formed from the base product fluid and three otherproduct formulations.

FIG. 25 depicts the average in the difference of total copper anddissolved copper from a 96-hour inhibition test for the differentinhibition concentrations and formulations depicted in FIG. 24.

FIG. 26 depicts percent mortality versus days of exposure for differentconcentrations of the end product (with concentrations expressed ascopper equivalent concentrations) made from the base product fluid.

FIG. 27 depicts average mortality of Aedes albopictus larvae after 24hours of exposure to various treatments of the end product.

While the disclosure is susceptible to various modifications andalternative forms, specific embodiments thereof are shown by way ofexample in the drawings and will herein be described in detail. Itshould be understood, however, that the drawings and detaileddescription thereto are not intended to limit the disclosure to theparticular form illustrated, but on the contrary, the intention is tocover all modifications, equivalents and alternatives falling within thespirit and scope of the present disclosure as defined by the appendedclaims. The headings used herein are for organizational purposes onlyand are not meant to be used to limit the scope of the description. Asused throughout this application, the word “may” is used in a permissivesense (i.e., meaning having the potential to), rather than the mandatorysense (i.e., meaning must). Similarly, the words “include,” “including,”and “includes” mean including, but not limited to. Additionally, as usedin this specification and the appended claims, the singular forms “a”,“an”, and “the” include singular and plural referents unless the contentclearly dictates otherwise. Furthermore, the word “may” is usedthroughout this application in a permissive sense (i.e., having thepotential to, being able to), not in a mandatory sense (i.e., must). Theterm “include,” and derivations thereof, mean “including, but notlimited to.” The term “coupled” means directly or indirectly connected.

The scope of the present disclosure includes any feature or combinationof features disclosed herein (either explicitly or implicitly), or anygeneralization thereof, whether or not it mitigates any or all of theproblems addressed herein. Accordingly, new claims may be formulatedduring prosecution of this application (or an application claimingpriority thereto) to any such combination of features. In particular,with reference to the appended claims, features from dependent claimsmay be combined with those of the independent claims and features fromrespective independent claims may be combined in any appropriate mannerand not merely in the specific combinations enumerated in the appendedclaims.

DETAILED DESCRIPTION OF EMBODIMENTS

The following examples are included to demonstrate preferredembodiments. It should be appreciated by those of skill in the art thatthe techniques disclosed in the examples which follow representtechniques discovered by the inventor to function well in the practiceof the disclosed embodiments, and thus can be considered to constitutepreferred modes for its practice. However, those of skill in the artshould, in light of the present disclosure, appreciate that many changescan be made in the specific embodiments which are disclosed and stillobtain a like or similar result without departing from the spirit andscope of the disclosed embodiments.

This specification includes references to “one embodiment” or “anembodiment.” The appearances of the phrases “in one embodiment” or “inan embodiment” do not necessarily refer to the same embodiment, althoughembodiments that include any combination of the features are generallycontemplated, unless expressly disclaimed herein. Particular features,structures, or characteristics may be combined in any suitable mannerconsistent with this disclosure.

Chelation is a type of bonding of metal ions to at least two nonmetalions that are components of a larger molecule. As used herein, bondingof metal ions to a chelant molecule can include any type of ionic bondor atomic attraction (e.g., hydrogen bonding). As used herein, achelating agent can include organic or inorganic molecules or molecularaggregates or ordered molecular assemblages capable of forming a stablecomplex with one or more metal ions.

FIG. 1 depicts a representation of an embodiment of a process system forproducing an embodiment of a base product fluid. In certain embodiments,process system 50 includes subsystems 100, 200, 300, 400, and 500. FIGS.2-6 depict detailed representations of embodiments of subsystems 100,200, 300, 400, and 500. Subsystems 100, 200, 300, 400, and 500 maycombine to produce a base product fluid with desired properties.

FIG. 2 depicts a detailed representation of an embodiment of subsystem100. Subsystem 100 may be a water and anhydrous liquid ammonia (NH₃)mixing system. In certain embodiments, subsystem 100 includes water tank102 and ammonia cylinder 104. Ammonia cylinder 104 may be an anhydrousliquid ammonia cylinder. Water tank 102 may be a water storage tank witha desired capacity. For example, water tank 102 may have a capacity ofabout 300 gallons. FIG. 7 depicts an example of an embodiment of watertank 102. As shown in FIG. 2, water tank 102 provides water into waterline 106. In some embodiments, water and/or water mixed with someadditional materials (e.g., ammonia and/or sulfuric acid) collected instart-up tank 504 of subsystem 500 (shown in FIG. 6) during startup ofprocess system 50 is added at 108.

Pump 110 may be used to control the flow of water through water line106. Pump 110 may be, for example, a metering pump or a variablefrequency drive pump. In some embodiments, pump 110 is a variablefrequency drive pump operating at a frequency between about 15 Hz andabout 55 Hz. In certain embodiments, the flowrate of water is controlledat a desired flowrate. For example, the flowrate of water may be betweenabout 0.5 gpm (gallons per minute) and about 3 gpm. In some embodiments,the flowrate of water is between about 0.65 gpm and about 2.5 gpm. Theflowrate of water may be adjusted to provide a different desired outputrate for product from system 50.

Ammonia cylinder 104 may be a pressure cylinder designed for use withanhydrous liquid ammonia. FIG. 8 depicts an example of an embodiment ofammonia cylinder 104. Ammonia cylinder 104 may have a weight of, forexample, 140 lbs. Scale 105 may be used to monitor a weight of ammoniacylinder 104. As shown in FIG. 2, ammonia cylinder 104 may provideanhydrous liquid ammonia into ammonia line 112. The anhydrous liquidammonia may be cooled using heat exchanger 114 located on ammonia line112. Heat exchanger 114 may be, for example, a heat exchanger thatcirculates cooling fluid from chiller 117 to cool the anhydrous liquidammonia flowing through the heat exchanger. In certain embodiments,chiller 117 circulates cooling fluid at a temperature below about 18° F.to maintain the ammonia as liquid ammonia at elevated pressures (e.g.,pressures above atmospheric pressure).

The flow of ammonia through ammonia line 112 may be controlled usingvalve 113 located on the ammonia line. Valve 113 may be, for example, aneedle valve. In some embodiments, the flowrate of anhydrous liquidammonia is between about 3 gph (gallons per hour) and about 15 gph. Insome embodiments, the flowrate of anhydrous liquid ammonia is betweenabout 3 gph and about 6 gph or between about 3 gph and about 5 gph. Thepressure of ammonia in ammonia line 112 may be controlled using pressureregulator 115. Pressure regulator 115 may be, for example, a forwardpressure regulator. In some embodiments, the pressure of ammonia isabout 60 psig. At a pressure of about 60 psig, heat exchanger 114 needsto cool the ammonia to a temperature of about 43° F. to maintain theammonia as liquid ammonia. The pressure of ammonia and/or thetemperature of cooling fluid from chiller 117 may be adjusted as desiredor needed to ensure ammonia flowing through heat exchanger 114 ismaintained as liquid ammonia. In some embodiments, ammonia line 112 isinsulated to maintain the ammonia in the liquid state (e.g., keep theammonia from boiling in the ammonia line).

In certain embodiments, liquid ammonia in ammonia line 112 is combinedwith water from water line 106 at junction 116 and the combinedammonia/water fluid enters process line 118. Using liquid ammonia(instead of ammonia gas) inhibits flashing of products of reactionbetween ammonia, sulfuric acid, and water. In certain embodiments, waterand ammonia are combined at a desired weight ratio. For example, in someembodiments, water and ammonia are combined with a weight ratio of about15.6:1 (water:ammonia). In some embodiments, the weight ratio of waterto ammonia is between about 10:1 and about 20:1, between about 12:1 andabout 18:1, or between about 14:1 and 16:1.

Process line 118 may provide the ammonia/water fluid to subsystem 200,shown in FIG. 3. FIG. 3 depicts a detailed representation of anembodiment of subsystem 200. Subsystem 200 may be a first reactorsystem. In certain embodiments, subsystem 200 is used to react theammonia/water fluid with a small (first) portion of sulfuric acid(H₂SO₄).

Sulfuric acid may be stored in acid tank 202. FIG. 9 depicts an exampleof an embodiment of acid tank 202. Acid tank 202 may be an acid storagetank with a desired capacity. For example, acid tank 202 may have acapacity of about 120 gallons. As shown in FIG. 3, acid tank 202provides acid (e.g., sulfuric acid) into acid line 204. Pump 206 may beused to control the flow of acid through acid line 204. Pump 206 may be,for example, a metering pump or a variable frequency drive pump. In someembodiments, pump 206 is a variable frequency drive pump operating at afrequency between about 15 Hz and about 55 Hz.

Acid line 204 may couple with process line 118 at junction 208 to addthe acid to the ammonia/water fluid. In some embodiments, acid in acidline 204 has a flowrate in a range between about 200 ml/min and about1200 ml/min, between about 500 ml/min and about 1200 ml/min, or betweenabout 600 ml/min and about 1000 ml/min. In certain embodiments, acid isadded to the ammonia/water fluid at a desired weight ratio. For example,in some embodiments, the ammonia/water fluid to acid weight ratio isabout 7.2:1. In some embodiments, the weight ratio of ammonia/waterfluid to acid is between about 5:1 and about 9:1, between about 6:1 andabout 8:1, or between about 6.5:1 and 7.5:1.

The combined acid/ammonia/water fluid may then flow through mixer 210.Mixer 210 may be, for example, a static mixer. A mixed fluid of acid,ammonia, and water may flow out of mixer 210 and be provided tosubsystem 300, shown in FIG. 4. In certain embodiments, the pH of thecombined acid/ammonia/water fluid in mixer 210 is controlled. Forexample, the pH of the combined acid/ammonia/water fluid in mixer 210may be controlled to be between a pH of about 1 and a pH of about 9.

FIG. 4 depicts a detailed representation of an embodiment of subsystem300. Subsystem 300 may be a heat exchanger system. In certainembodiments, subsystem 300 includes heat exchanger 302 in-line withprocess line 118. Heat exchanger 302 may cool the mixed fluid as themixed fluid flows through the heat exchanger. Cooling of the mixed fluidmay be needed as the mixing of the ammonia/water fluid with sulfuricacid is exothermic. Cooling fluid 304 may be circulated through heatexchanger 304 to cool the mixed fluid. In certain embodiments, coolingfluid 304 is water. In some embodiments, cooling fluid 304 enters heatexchanger 302 at a temperature of at most about 65° F. and circulatesthrough the heat exchanger at a flow rate of at least about 5 gpm(gallons per minute).

In certain embodiments, heat exchanger 302 cools the mixed fluid by atleast about 50° F., by at least about 75° F., or by at least about 150°F. For example, heat exchanger 302 may cool the mixed fluid from atemperature of about 200° F. to a temperature of about 75° F. In someembodiments, heat exchanger 302 cools the mixed fluid from a temperatureof about 225° F. to a temperature of about 75° F.

In some embodiments, pulsation dampener 306 is coupled to process line118 downstream of heat exchanger 302. After pulsation dampener 306,process line 118 may provide the (cooled) mixed fluid to subsystem 400,shown in FIG. 5. FIG. 5 depicts a detailed representation of anembodiment of subsystem 400. Subsystem 400 may be a second reactorsystem. In certain embodiments, subsystem 400 is used to add and reactadditional sulfuric acid (e.g., a second portion of sulfuric acid) tothe mixed fluid.

Sulfuric acid may be stored in acid tank 402. FIG. 10 depicts an exampleof an embodiment of acid tank 402. Acid tank 402 may be an acid storagetank with a desired capacity. For example, acid tank 402 may have acapacity of about 500 gallons. As shown in FIG. 5, acid tank 402provides acid (e.g., sulfuric acid) into acid line 404. Pump 406 may beused to control the flow of acid through acid line 406. Pump 406 may be,for example, a metering pump or a variable frequency drive pump. In someembodiments, pump 406 is a variable frequency drive pump operating at afrequency between about 15 Hz and about 55 Hz.

Acid line 404 may couple with process line 118 at junction 408 to addthe additional acid to the mixed fluid. In some embodiments, acid inacid line 404 has a flowrate in a range between about 1000 ml/min andabout 5000 ml/min, between about 1100 ml/min and about 4900 ml/min, orbetween about 1200 ml/min and about 4800 ml/min. The new mixed fluid maythen flow through mixer 410. In certain embodiments, the new mixed fluidhas a pH of about zero. Mixer 410 may be, for example, a static mixer. Amixed fluid of acid, ammonia, and water may flow out of mixer 410 and beprovided to subsystem 500, shown in FIG. 6.

In certain embodiments, as shown in FIG. 5, valve 412 is used to controla pressure of the mixed fluid as the fluid flows through process line118. Controlling the pressure at valve 412 may control the pressure inprocess line 118 (e.g., adjusting the pressure at valve 412 adjusts thesystem pressure in subsystems 100-400). Valve 412 may be, for example, aneedle valve. In some embodiments, valve 412 is used to adjust thesystem pressure after sulfuric acid addition begins in subsystem 200(shown in FIG. 3) and/or subsystem 400 (shown in FIG. 5). In certainembodiments, the system pressure is between about 40 psig and about 80psig. Other system pressures may also be used as needed or desired.

In certain embodiments, the additional (second) portion of sulfuric acidadded in subsystem 400 (shown in FIG. 5) is larger than the (first)portion of sulfuric acid added in subsystem 200 (shown in FIG. 3). Forexample, a ratio of the second portion of sulfuric acid to the firstportion of sulfuric acid by weight is about 6:1. In some embodiments,the ratio of the second portion of sulfuric acid to the first portion ofsulfuric acid by weight is between about 2:1 and about 7:1, betweenabout 3:1 and about 6:1, or between about 3.5:1 and about 5.5:1.

FIG. 6 depicts a detailed representation of an embodiment of subsystem500. Subsystem 500 may be a product system. In certain embodiments,subsystem 500 includes product tank 502 and start-up tank 504. Producttank 502 may be a storage tank with a desired capacity. For example,product tank 502 may have a capacity of about 20000 gallons. Producttank 502 may be used to collect a base product fluid produced by system50 (e.g., the mixed fluid produced after the addition of the secondportion of sulfuric acid).

FIG. 11 depicts an example of an embodiment of start-up tank 504. Asshown in FIGS. 1 and 6 , start-up tank 504 may be used to collect fluidsduring start-up periods of system 50. Start-up periods of system 50 maybe periods before the base product fluid with desired properties isproduced. For example, start-up periods of system 50 may include periodsbefore the second portion of sulfuric acid is added to the mixed fluidin subsystem 400, shown in FIG. 5. Thus, start-up periods of system 50may include times (periods) for bringing water and/or ammonia up todesired pressures and/or flowrates without the addition of any sulfuricacid. Addition of the first portion of sulfuric acid (in subsystem 200depicted in FIG. 3) may also be part of a start-up period as well as anyramp-up portion of adding the second portion of sulfuric acid to themixed fluid (in subsystem 400 depicted in FIG. 5) (e.g., ramp-up ofadding the second portion before stable (steady-state) conditions existin the system).

As the desired base product fluid is not produced during these times,the fluids produced during the start-up periods may be collected andstored in start-up tank 504. In some embodiments, fluids stored instart-up tank 504 are recycled into water line 106 at 108 in subsystem100, as shown in FIG. 2. For example, fluids collected before anysulfuric acid is added (e.g., fluids of water and ammonia) may beprovided into water line 106 and used as part of the water/ammonia feedfor system 50. In some embodiments, fluids stored in start-up tank 504are drained.

After the start-up period ends, product flow in subsystem 500, shown inFIG. 6, may be switched from start-up tank 504 to product tank 502.After switching flow between the tanks, pressure in the system may needto be adjusted to return the system to stable (steady-state) conditions.

In certain embodiments, temperatures, pressures, and/or pH levels aremonitored at one or more locations in system 50. Temperatures,pressures, flowrates, and/or pH levels may be monitored using sensorslocated along process line 118 and/or other lines (e.g., water linesand/or acid lines) in system 50. For example, temperatures may bemonitored using temperature sensors 52, pressures may be monitored usingpressure sensors 54, flowrates may be monitored using flowrate sensors56 (e.g., mass flow controllers), and pH level may be monitored using pHmonitors 58, shown in FIGS. 1-6. Data from these sensors may be used tomonitor and/or control the operation of system 50.

As shown above, system 50 may be used to produce a base product fluidfrom a mixture of water, ammonia, and sulfuric acid. In certainembodiments, system 50 produces the base product fluid at desiredoutputs and stores/collects the base product fluid in product tank 502.For example, system 50 may produce between about 1 gpm (gallon perminute) and about 4 gpm of the base product fluid under steady-state(stable) conditions (e.g., under steady-state conditions when the secondportion of sulfuric acid is being added to the mixed fluid). Otherdesired outputs of the base product fluid may be produced by system 50by adjusting one or more properties of the system. Properties that maybe adjusted include, but are not limited to, flowrates of water,ammonia, and/or sulfuric acid, pressures, pH, and temperatures. In someembodiments, the sizes of piping, tanks, valves, etc. may also need tobe adjusted to produce different desired outputs from system 50.

In certain embodiments, orifice mixers are used instead of or along withmixer 210, depicted in FIG. 3, to provide different mixing betweenwater, ammonia, and the first portion of sulfuric acid in subsystems 100and 200, depicted in FIGS. 2 and 3, respectively. For example, orificemixers may be provided inline to mix fluids during or after when onefluid is injected into another fluid. In some embodiments, the sizesand/or locations of the orifice mixers are varied along with variationsin the size, location, and/or number of mixer 210 (e.g., static mixer),depicted in FIG. 3. Variations of the number, size, and/or locations ofthe orifice mixers and/or the static mixers may provide differentdesirable properties in the base product fluid produced by system 50.

FIGS. 12A-F depicts various mixer configurations of orifice mixers andstatic mixers suitable for use in system 50 to provide differentproperties in the base product fluid. FIG. 12A depicts a mixerconfiguration with orifice mixer 600 positioned in process line 118immediately after water (from water line 106) is combined with ammonia(from ammonia line 112) and before sulfuric acid (from acid line 204) isadded to the water/ammonia mixture. Orifice mixer 600 may be, forexample, a 0.3″ orifice mixer. FIG. 12B depicts a variation of the mixerconfiguration in FIG. 12A with a second orifice mixer 600′ positioned inprocess line 118 immediately after sulfuric acid is added. In addition,static mixers 210 and 210′ are positioned after second orifice mixer600′. Second orifice mixer 600′ may be, for example, a 0.4″ orificemixer. Static mixer 210 may be a 3 element static mixer while staticmixer 210′ may be a 5 element static mixer.

FIG. 12C depicts a variation of the mixer configuration in FIG. 12B withfirst orifice mixer 600 removed and ammonia (from ammonia line 112) nowinjected at the same location as sulfuric acid (e.g., using a longinjector for the ammonia). FIG. 12D depicts a variation of the mixerconfiguration in FIG. 12C with ammonia (from ammonia line 112) injectedat the same location as sulfuric acid with a short length injector. FIG.12E depicts a variation of the mixer configuration in FIG. 12D withammonia (from ammonia line 112) injected downstream of the sulfuric acidwith a short length injector. FIG. 12F depicts a variation of the mixerconfiguration in FIG. 12E with ammonia (from ammonia line 112) injecteddownstream of first static mixer 210 and no orifice mixers.

The base product fluid, produced by system 50 and its related processdescribed above in the embodiments of FIGS. 1-12, is a metal chelatingagent that shows improved properties compared to other water, ammonia,and sulfuric acid based metal chelating agents.

The base product fluid may have selected properties due to clustering ofmolecular compounds of ammonium sulfate, ammonium bisulfate, sulfuricacid, and/or water in the base product fluid. In certain embodiments,the clusters of molecular compounds have a variety (plurality) of sizes.Examples of ammonium sulfate, ammonium bisulfate, and sulfuric acid aregiven in: Joseph W. DePalma et al. (2012): Structure and Energetics ofNanometer Size Clusters of Sulfuric Acid with Ammonia and Dimethylamine,The Journal of Physical Chemistry, 116, 1030-1040, which is incorporatedby reference as if fully set forth herein.

Aqueous size-exclusion high-performance liquid chromatography (SE-HPLC)tests on the base product fluid were performed to separate thecomponents in the base product fluid. FIG. 13 depicts a 210 nmchromatogram of the base product fluid using SE-HPLC. As shown in FIG.13, the base product fluid chromatogram has 5 different peaks showingdifferent molecular weight structures are present in the base productfluid. These different molecular weight structures may be due toclustering in the base product fluid.

FIG. 14 depicts a plot of infrared (IR) spectra comparing the baseproduct to ammonium bisulfate ((NH₄)HSO₄). Plot 700 is an IR spectrumfor ammonium bisulfate powder. Plot 702 is an IR spectrum for a solidbase product. The solid base product may be isolated from the baseproduct fluid (e.g., the base product fluid is dehydrated to form thesolid base product). The IR spectrum were obtained on a Nicolet1550-FT-IR spectrophotometer with a Smart iTR for solid and liquidsamples. As shown in FIG. 14, plot 702 for the base product fluidincludes several IR bands characteristic of ammonium bisulfate.

Elemental analysis of the solid base product shows that that onlynitrogen, oxygen, sulfur, and hydrogen are present in the base product.TABLE 1 shows elemental analysis mass percentages of the base productalong with elemental mass percentages for possible components of thebase product (ammonium bisulfate, ammonium sulfate, sulfuric acid, andwater):

TABLE 1 ELE- BASE MENT PRODUCT (NH₄)HSO₄ (NH₄)₂SO₄ H₂SO₄ H₂O HYDRO-4.70% 4.38% 6.10%  2.06% 11.19% GEN NITRO- 14.80% 12.17% 21.20% — — GENSULFUR 26.55% 27.85% 24.26% 32.69% — OXYGEN 53.95% 55.60% 48.43% 65.25%88.81%

As shown in TABLE 1, the base product fluid has elemental masspercentages that do not match elemental mass percentages associated withany of the possible components. Thus, the base product fluid may be acompound having these possible components in various amounts.

X-ray photoelectron spectroscopy (XPS) was also performed on the solidbase product to confirm results of the elemental analysis. XPS wasconducted on the base product using a Physical Electronics 5800 multianalysis tool. The survey scans were run at a step size of 1.6 eVresolution and a pass energy of 187.85 eV. The High Resolution spectrawere taken at a pass energy of 23.5 eV and a step size of 0.1 eV. A lowenergy dispersed electron beam shower was used to neutralize the sampleand used the C 1 s, adventitious carbon, at 284.8 eV to shift the HighResolution spectra to this peak as a “standard”. TABLE 2 displays theatomic percentage results of the XPS analysis.

TABLE 2 BASE PRODUCT Atomic % High (NH₄)HSO₄ (NH₄)₂SO₄ NormalizedResolution Atomic % Survey XPS XPS Theoretical Theoretical NITROGEN 18.018.2 16.66 28.57 OXYGEN 65.9 64.6 66.66 57.17 SULFUR 16.1 17.2 16.6614.28

As shown in TABLE 2, XPS data confirms the elemental analysis resultsthat only nitrogen, oxygen, and sulfur (along with hydrogen) are presentin the base product. XPS also showed that substantially all the nitrogenin the base product is in an oxidation state of −3 (oxidation state fornitrogen in ammonia) and substantially all the sulfur in the baseproduct is in an oxidation state of +6 (oxidation state for sulfur insulfate/bisulfate).

FIG. 15 depicts plots of X-ray diffraction analysis (XRD) spectracomparing the solid base product to ammonium bisulfate ((NH₄)HSO₄) andammonium sulfate ((NH₄)₂SO₄). Plot 704 is an XRD spectrum for ammoniumbisulfate. Plot 706 is an XRD spectrum for the base product fluid. Plot708 is an XRD spectrum for ammonium sulfate. Plot 706, while having somepeaks identical to plots 704 and 708, also includes other peaks notfound in the other plots. Thus, the XRD spectra shown in FIG. 15indicate that the base product fluid is not ammonium bisulfate orammonium sulfate.

FIG. 16 depicts time-of-flight mass spectrometry (TOFMS) of the baseproduct fluid. TOFMS was conducted using a nano ESI MS using Q-TofPremier from Waters with MassLynx 4.1 software to control theacquisition and data analysis. The base product fluid sample wasinjected as is and analyzed in both positive and negative ion mode (Vmode). The source parameters were: Positive ion mode, Capillary 0.1-1kV, Sampling cone 74V, Extraction cone 3.6V and Ion Guide 2.5V. As shownin FIG. 16, multiple ammonium bisulfate units fragment off the baseproduct fluid, which may indicate that the number of ammonium bisulfateunits may vary between compounds in the base product fluid.

Additional mass spectrometry of the base product fluid was conductedusing high-resolution electrospray mass spectral analysis to assess ahigher mass range with increased resolution. The high-resolutionelectrospray mass spectral analysis was conducted using a nano ESI(electrospray ionization) MS using TOF/Q-TQF on an Agilent TechnologiesMass Spectrometer. The base product fluid sample was injected as is andanalyzed in both positive and negative ion mode (V mode). The sourceparameters were: Vcap 3500, Corona Positive 2.0, Fragmentor 75, Skimmer160.0, and Octopole RF Peak 250. FIG. 17 depicts a high-resolution massspectrum of the base product fluid for masses 100-800. FIG. 18 depicts ahigh-resolution mass spectrum of the base product fluid for masses700-1600.

The data shown in FIGS. 17 and 18 may imply a slightly differentstructure than the data shown in FIG. 16. In ESI MS analysis, the parentpeak of the compound may often be protonated once or multiple times. Ina base product fluid sample with a pH of about 2.5, there are protonsavailable to protonate the base product compound. For example, the peakat about mass 937 is a major peak in both FIG. 16 and FIG. 18 (e.g., inboth low resolution and high resolution mass spectrum). In FIG. 18,however, the exact mass shown is 937.9874, which is slightly differentfrom the exact mass calculated for a compound of((NH₄)₂SO₄)₁.(H₂SO₄)₁.(H₂O)₁.(NH₄HSO₄)₆ as shown in TABLE 3.

TABLE 3 ((NH₄)₂SO₄)₁•(H₂SO₄)₁•(H₂O)₁•(NH₄HSO₄)₆ Exact Mass H 42 1.00782542.32865 N 8 14.00307 112.02456 S 8 31.97207 255.77656 O 33 15.99492527.83236 937.96213

The high-resolution mass spectrum shown in FIGS. 17 and 18 support thefollowing structure for the 937 peak:((NH₄)₂SO₄)₂.(H₂SO₄)₁.(H₂O)₀.(NH₄HSO₄)₅H⁺ is 937.98593, as shown inTABLE 4. The H⁺ in the structure is added from the electrospraytechnique and not part of the compound itself. A similar analysis may beconducted for all the peaks in the high-resolution mass spectrum shownin FIGS. 17 and 18.

TABLE 4 ((NH₄)₂SO₄)₂•(H₂SO₄)₁•(H₂O)₀•(NH₄HSO₄)₅•H⁺ Exact Mass H 431.007825 43.336475 N 9 14.00307 126.02763 S 8 31.97207 255.77656 O 3215.99492 511.83744 937.98593

The difference in the masses of the major peaks in the high-resolutionmass spectrum averaged 114.9942. The exact mass of ammonium bisulfate(NH₄HSO₄) is 114.9939. Therefore, in certain embodiments, the formula ofthe base product fluid may be represented as((NH₄)₂SO₄)_(a).(H₂SO₄)_(b).(H₂O)_(c).(NH₄HSO₄)_(x), where a is between1 and 5, b is between 1 and 5, c is between 0 and 5, and x is between 1and 20.

It should be noted that at least some of the experimental data describedabove is assessed on a solid form of an “intermediate” of the baseproduct fluid. In certain embodiments, the intermediate of the baseproduct fluid is the fluid produced after the reaction of liquidammonia, sulfuric acid, and water but before the addition of the secondportion of sulfuric acid. For example, the intermediate of the baseproduct fluid is fluid removed from process line 118 between subsystem300 and subsystem 400, shown in FIG. 1. Water can be removed from theintermediate of the base product fluid to form a solid form of theintermediate. The solid form may then be assessed to provide theexperimental data described above. Using the intermediate of the baseproduct fluid for providing experimental data may be needed as, in manycases, the base product fluid produced by system 50 (e.g., the productafter the second portion of sulfuric acid is added) is too corrosive formuch of the equipment used to assess experimental data (e.g., massspectrometers, XRD equipment, XPS equipment, and/or IR equipment).

While the experimental data described above is assessed on theintermediate of the base product fluid, it is believed that the dataassessed for the intermediate may reasonably correlate to expected datafor the base product fluid itself as the intermediate may be a molecularcompound found in the base product fluid. For example, the base productfluid is a product of the intermediate with additional sulfuric acid(and water) and it may reasonably be postulated that the base productincludes the intermediate with additional sulfuric acid and watermolecules. Based on the above experimental data for the intermediate ofthe base product fluid, the intermediate may be described to bemolecular compounds having various amounts of ammonium sulfate, ammoniumbisulfate, sulfuric acid, and water with the molecular compounds beingin cluster-type formations. Combining the intermediate with additionalsulfuric acid to form the base product fluid increases the amount ofsulfuric acid and water available for clustering. Additionally,clustering between clusters of the intermediate may also be possiblewith the addition of sulfuric acid and water (e.g., the additionalsulfuric acid and water may facilitate clustering between compounds inthe intermediate). It may be reasonable to postulate that the baseproduct fluid includes the same cluster-type formations found in theintermediate, only with larger cluster/particle sizes being possible inthe base product fluid due to the additional sulfuric acid and water.The intermediate may, for example, conglomerate with sulfuric acidand/or water to produce larger clusters/particles. Thus, the baseproduct fluid may possibly be described as a compound formed of theclusters of the intermediate (as described by the experimental data)along with additional sulfuric acid and water.

Based on the experimental data and the above postulations regarding thestructure of the base product fluid, a molecular compound in the baseproduct fluid may be described as a clustered combination of ammoniumsulfate, ammonium bisulfate, sulfuric acid, and water. In someembodiments, the molecular compound in the base product fluid issubstantially similar in structure to the intermediate of the baseproduct fluid described above (e.g., the molecular compound may bedescribes as being substantially the intermediate). In certainembodiments, the molecular compound in the base product fluid isdescribed by the formula:((NH₄)₂SO₄)_(a).(H₂SO₄)_(b).(H₂O)_(c).(NH₄HSO₄)x with a, b, c, and xvarying between molecular compounds in the base product fluid dependingon cluster sizes of the molecular compounds. In certain embodiments, ais at least 1, b is at least 1, c is at least 0, and x is at least 1 inthe formula for the molecular compound in the base product fluid. Incertain embodiments, a is between 1 and 5, b is between 1 and 5, c isbetween 0 and 5, and x is between 1 and 20. In some embodiments, a isbetween 1 and 5, b is between 1 and 5, c is between 0 and 5, and x isbetween 1 and 15. In some embodiments, a is between 1 and 5, b isbetween 1 and 5, c is between 1 and 5, and x is between 1 and 10. Insome embodiments, a is between 1 and 3, b is between 1 and 3, c isbetween 1 and 3, and x is between 1 and 6. In one embodiment, the baseproduct fluid includes a molecular compound having the formula:((NH₄)₂SO₄)₁.(H₂SO₄)₁.(H₂O)₁.(NH₄HSO₄)_(x); where x is between 1 and 20.

In certain embodiments, the molecular compound in the base product fluidhas the formula: ((NH₄)₂SO₄)_(a).(H₂SO₄)_(b).(H₂O)_(c).(NH₄HSO₄)_(x);with a mass percentage of hydrogen being between about 3% and about 6%,a mass percentage of nitrogen being between about 10% and about 15%, amass percentage of sulfur being between about 25% and about 30%, and amass percentage of oxygen being between about 52% and about 60%. In suchembodiments, a is at least 1, b is at least 1, c is at least 1, and x isat least 1 for the molecular compound. In some embodiments, themolecular compound in the base product fluid has the formula:((NH₄)₂SO₄)_(a).(H₂SO₄)_(b).(H₂O)_(c).(NH₄HSO₄)_(x); with a masspercentage of hydrogen being between about 4% and about 5%, a masspercentage of nitrogen being between about 11% and about 15%, a masspercentage of sulfur being between about 26% and about 28%, and a masspercentage of oxygen being between about 53% and about 57%. In oneembodiment, the molecular compound in the base product fluid has theformula: ((NH₄)₂SO₄)_(a).(H₂SO₄)_(b).(H₂O)_(c).(NH₄HSO₄)_(x); with amass percentage of hydrogen being about 4.7%, a mass percentage ofnitrogen being about 14.8%, a mass percentage of sulfur being about26.5%, and a mass percentage of oxygen being about 54%.

The molecular compound described above may be a chelating compound formetal salts (e.g., copper salts) in the base product fluid (e.g., themolecular compound is a metal chelating agent). As described herein, theterm “metal salt”, in addition to referring to a metal salt, may referto any other chemical composition or potential source of metal thatallows a metal to complex with a chelating compound (e.g., the molecularcompound). Examples of other potential sources of metals include, butare not limited to, non-salt metal complexes and electrolytic generationof ionic metal species (e.g., electrolytic generation of Cu++). Havingthe molecular compound in the base product fluid, as evidenced by theabove experimental data, may provide improved properties in the baseproduct fluid produced by system 50. For example, in some embodiments,the molecular compound may increase the rate of diffusion in water ofcopper and/or other metals added to the base product fluid. In someembodiments, the molecular compound may improve the transport of copperand/or other metals across a cell membrane when they are added to thebase product fluid. The improved transport may increase thebioavailability and/or reactivity of the metal (e.g., copper) in an endproduct formed from the base product fluid. The increasedbioavailability and/or reactivity may increase the effectiveness of theend product formed from the base product fluid. Increasing theeffectiveness of the end product may allow smaller doses of the endproduct to be used for desired results (e.g., desirable results invarious treatments in water-based systems). Additionally, unliketraditional chelating agents, the base product fluid with the molecularcompound does generate heat with the addition of metals or metal saltsto the base product fluid. The lack of heat generation may be anindicator of the absence of any coordination chemistry reactivity in thebase product fluid.

A diffusion testing apparatus was used to assess the diffusionefficiency of copper in water using the base product fluid with themolecular compound described above. FIG. 19 depicts a side-viewrepresentation of a copper diffusion testing apparatus. Testingapparatus 800 includes pipe 802. Pipe 802 is a PVC pipe with PVC endcaps 804 placed on each end of the pipe. Pipe 802 has an inside diameterof 10.16 cm and is 158.75 cm long end-to-end.

Ports 806 are used for sample addition into pipe 802 and samplecollection from the pipe. Ports 806 are 10 mm diameter openings spaced30 cm apart. Ports 806′ are closest to the ends of pipe 802 and are4.375 cm from the ends of the pipe. Pipe 802 was leveled and filled with12.0 L of water and allowed to stabilize for 48 hours before testing.The water temperature ranged from 24.5° C. to 26.5° C. Results obtainedin preliminary studies demonstrated that the first sampling point, e.g.,30 cm from the addition location, provided the most useful informationrelative to diffusion kinetics of test fluids. Efficiency of dispersionwas evaluated by comparing concentrations for all sampling locations atthe termination of each study.

After the stabilization period, an appropriate volume of a test fluidwas added to pipe 802. Two test fluids were assessed in apparatus 800.The first test fluid was an end product formed by the addition of coppersulfate pentahydrate to the base product fluid produced by system 50.The first test fluid had an undiluted volume of 202.7 μL and was 5% on aweight basis copper. The second test fluid was a 5% (on a weight basisof copper) prepared with copper sulfate pentahydrate with reverseosmosis water and acidified by adding 20 μL of 93% sulfuric acid per 100mL of solution. The second test fluid had an undiluted volume of 212.4μL.

Samples were then collected after selected incubation times. Theincubation times included no external mixing of the water (e.g., pipe802 is a static water system). Mixing via thermal currents was minimizedby maintaining the test apparatus at 25±1° C. in a climate controlledroom. Samples were collected via micropipetter from 2.5 cm below thesurface of the water. At the end of the test, samples were alsocollected from about 0.5 cm above the bottom of the water. FIG. 20depicts a cross-section end view of pipe 802 with water 808 in the pipeshowing sample collection locations 810 and 812. Location 810 is forsample collection via micropipetter from 2.5 cm below the surface ofwater 808. Location 812 is for sample collection from about 0.5 cm abovethe bottom of water 808 at the end of the study.

FIG. 21 depicts plots of copper concentration versus time at the 30 cmsampling location for the chelated copper described herein, designatedESL-Cu, and copper sulfate, designated CuSO₄. FIG. 22 depicts surfacediffusion profiles of ESL-Cu and CuSO₄ after a 72-hour hold-time. timeversus distance from addition point for the first test fluid. FIG. 23depicts the bottom concentration diffusion profiles of ESL-Cu and CuSO₄after a 72-hour hold-time. As shown in FIGS. 21-23, copper in the ESL-Cutreated water disperses more quickly, more uniformly, and at higherconcentrations than that in the CuSO₄ treated water.

In certain embodiments, the end product formed from the base productfluid may show improved inhibition results in water tests. FIG. 24depicts inhibition concentrations for 25 percent reduction (IC₂₅) and 50percent reduction (IC₅₀) in reproduction or growth using the end productformed from the base product fluid and three other product formulations.Points 150A (IC₂₅) and 150B (IC₅₀) are for an end product formed fromthe base product fluid produced by system 50.

Points 152A (IC₂₅) and 152B (IC₅₀) are for a product formed by addingthe 88 gram solution of copper sulfate pentahydrate and water to 12grams of a synthetic formulation. The synthetic formulation is made bydissolving ammonium sulfate (72.4 grams) into distilled water (275.3grams) and then adding 98% sulfuric acid (230.4 grams) slowly withcooling to hold the maximum temperature during sulfuric acid addition to118° F. This synthetic formulation produces a product similar to the“cold process” metal chelating agent.

Points 154A (IC₂₅) and 154B (IC₅₀) are for a product formed by addingthe 88 gram solution of copper sulfate pentahydrate and water to 12grams of Sorber Acid (described above). Points 156A (IC25) and 156B(IC₅₀) are for a product formed by adding 20 grams of copper sulfatepentahydrate to 80 grams of distilled water.

As shown in FIG. 24, the end product produced from the base productfluid (points 150A, 150B) show improved inhibition concentrations ascompared to other product formulations (e.g., other metal chelatingagents). FIG. 25 depicts the average in the difference of total copperand dissolved copper from a 96-hour inhibition test for the differentinhibition concentrations and formulations depicted in FIG. 24. As shownin FIG. 25, the end product produced from the base product fluid (points150A, 150B) shows increased uptake of copper by the target speciesduring the inhibition test.

In certain embodiments, the base product fluid, produced by system 50and its related process described above in the embodiments of FIGS.1-12, has a low pH (typically around 0 pH) when in a water solution(e.g., when the base product fluid includes the molecular compoundsmixed with water). In certain embodiments, the base product fluid has apH of at most about 2 when mixed with water. In some embodiments, thebase product fluid has a pH of between about 0 and about 2 or betweenabout 0.4 and about 1 when mixed with water. In certain embodiments, asolid base product (or powdered base product) is isolated from the baseproduct fluid (e.g., the base product fluid is dehydrated to form asolid base product). In some embodiments, the solid base product isisolated from the base product fluid when the pH of the base productfluid is between about 0.4 and about 1. The solid base product may berehydrated (e.g., water added) to reconstitute the base product fluidwithout affecting the properties of the original base product fluid(e.g., the base product fluid before isolation of the solid baseproduct). With the low pH of the base product fluid when mixed withwater, the solid base product and/or the base product fluid may not beacutely toxic to skin and is useable in water-based treatment systems.

The base product fluid has certain desired properties that, whencombined with one or more other products, provide desirable propertiesfor various treatments in water-based systems. For example, the baseproduct fluid may be combined with copper sulfate pentahydrate(CuSO₄.5H₂O) and water to form an end product. In certain embodiments,the end product is formed by combining the copper sulfate pentahydrateand water in an approximately 0.3:1 ratio and then combining thatmixture with the base product fluid in an approximately 7.33:1 ratio.The resulting end product may have a copper concentration of about 57μg/μL (about 4.8% copper by weight) after the addition of copper sulfateand water to the base product fluid. In some embodiments, the endproduct is between about 5% and about 15% by weight base product fluid.For example, the end product may be about 12% by weight base productfluid. The end product may be used in water-based treatment systems suchas, but not limited to, swimming pools, wastewater lagoons, storagereservoirs, decorative fountains, cooling water, irrigation canals,ornamental lakes, ponds, lagoons, reservoirs, water features on golfcourses, retention ponds, detention ponds, natural and artificial lakes,impoundments, estuaries, streams, and rivers, municipal and/orcommercial water treatment systems, zebra mussel treatment systems,agricultural water treatment systems (e.g., control of tadpole shrimp),and irrigation lines (e.g., keeping drip irrigation lines open and freefrom algae and bacteria).

In certain embodiments, the base product fluid is used to produce an endproduct that controls nuisance mollusks or bivalves such as zebramussels and quagga mussels, crustaceans, and biofouling invertebrates.The end product may be formed by adding copper sulfate and water to thebase product fluid. The end product may be placed at a location of amollusk infestation or in an area to prevent mollusk infestation. Insome embodiments, the end product is applied to open waters such aslakes, ponds, or reservoirs, to flowing waters such as pipelines, or toclosed systems such as cooling systems or fire suppression systems. Aneffectiveness of the end product may depend on ambient water conditionssuch as, but not limited to, temperature, alkalinity, hardness, andtotal organic carbon (TOC).

For open water treatment, the end product may be applied directly to thebody of water being treated. In some embodiments, the end product isapplied at the water surface and allowed to disperse. Because of thehigh diffusion rate provided by the base product fluid, metal or metalsalts may disperse readily in stagnant (static) water systems. In someembodiments, the end product is directed to a specific location (e.g.,at or near a pipe input) via hoses, pumps, diffusers, etc.

For flowing water treatment, the end product may be providedcontinuously into or on the flowing water. The end product may be usedas a curative measure when adult or juvenile mollusks already exist (forwhich a higher initial dose may be needed) or as a preventative measureto inhibit colonization. For closed systems, the end product may beapplied directly into a source for water in the system (e.g., a sourceor supply tank or reservoir).

For the treatment of mussels, the end product may be provided to thewater system at a “lethal concentration” (e.g., a concentration thatprovides about 100% mortality of the mussels in a given time period).Previous tests have shown that treatment of mussels using other copperbased treatments was ineffective at copper equivalent levels of 0.5 mg/l(500 ppb). These previous tests are demonstrated in: Ashlie Watters etal. (2012): Effectiveness of EarthTec® for killing invasive quaggamussels (Dreissena rostriformis bugensis) and preventing theircolonization in the Western United States, Biofouling: The Journal ofBioadhesion and Biofilm Research, 29:1, 21-28; and Renata Claudi M.Sc.et al., “Efficacy of Copper Based Algaecides for Control of Quagga andZebra Mussels”, January, 2014, which are both incorporated by referenceas if fully set forth herein.

The end product made from the base product fluid produced by system 50,however, shows lethal effectiveness at lower copper equivalent levels.FIG. 26 depicts percent mortality of mussels versus days of exposure fordifferent concentrations of the end product (with concentrationsexpressed as copper equivalent concentrations) made from the baseproduct fluid produced by system 50. As shown in FIG. 26, the endproduct shows full mortality in less than 10 days for copper equivalentlevels down to 57 ppb (0.057 mg/l). The copper equivalent level of 57ppb may be achieved using a 1 ppm concentration of the end product.

In some cases, the end product may show mortality at longer times (e.g.,20-30 days) for copper equivalent levels as low as 26 ppb. The data for26 ppb shown in FIG. 26 was terminated early (at 80% mortality) due tochanges in the lake level and a consequent disruption in the pipeline'sflow. Nevertheless, it is believed that full mortality may be achievedwith 26 ppb copper equivalent level at normal summer temperatures.Treatment for mussels at the copper equivalent levels shown in FIG. 26(e.g., below about 171 ppb copper equivalent level) may allow the endproduct to be used as a viable alternative to chlorine or othertreatments used for mollusk control.

In some embodiments, the end product for mollusk control is formed froma solid base product. For example, the base product fluid produced bysystem 50 may be dehydrated to form a solid or powdered base product. Insome embodiments, the base product fluid is dehydrated to form the solidor powdered base product when the pH of the base product fluid isbetween about 0.4 and about 1, as described above. Water may be added tothe solid base product to rehydrate and re-liquefy the base product. Insome embodiments, the solid base product is formed into a solid shapesuch as a puck. In some embodiments, the powdered base product is mixedwith copper sulfate powder. The powdered base product and copper sulfatemix may be formed into a solid shape or delivered using a metereddelivery system to the treatment site. The powdered base product andcopper sulfate mix may then activate (rehydrate) when added to the water(e.g., the water being treated for mollusks).

In some embodiments, the base product fluid is used to produce an endproduct that is used to remove taste and odor compounds and/ormicroorganisms from drinking water (e.g., municipal drinking water). Acommon result of algae blooms in water, which may be eventually used fordrinking water, is the formation of two compounds: geosmin and methyliso-borneol (MIB). Geosmin and MIB, at concentrations in the ppt (partsper trillion) range may give water an objectionable earthy taste and/orodor. Current treatment options for taste and odor include high chlorinedosage, which is problematic in that carcinogenic chlorine by-productsare formed, and powder activated carbon, which may be expensive.

The treatment of water for taste and/or odor using the end product maynot involve a mechanism utilizing the copper in the end product. Removalof taste and/or odor from the water may be due to UV absorbing compoundsfound in the base product fluid and thus, the end product. In someembodiments, the end product is provided at a dose level of 1 ppm, whichresults in a copper equivalent level of about 57 ppb. Other dose levelsmay be used as desired and/or the end product may have a different(e.g., lower) concentration of copper as desired.

In some embodiments, the base product fluid is used to produce an endproduct for control and/or elimination of microorganisms in watersystems. For example, the end product may be used to control and/oreliminate microorganisms in heat exchangers, metalworking fluids,reverse osmosis water processing, oil and gas field injection,fracturing, produced water, oil, and gas from wells and reservoirs,deaeration tower, oil and gas operation and transportation systems, oiland gas separation systems and storage tanks, oil and gas pipelines, gasvessels, toilet bowls, swimming pools, household drains, householdsurfaces, process equipment, sewage systems, wastewater and treatmentsystems, other industrial process water, boiler systems, ballast waterand equipment, pipes, tubes, and other surfaces in these systems.

In some embodiments, the base product fluid is used to produce an endproduct that is used as a mosquito killer (e.g., “mosquito-cide”).Copper sulfate is known to kill mosquitoes. However, achieving aneffective dose of copper (II) ions for killing mosquitoes may require asignificant amount of copper sulfate and most of the copper sulfate(about 90%) may end up in a non-reactive solid as sludge on the bottomof the lake or water reservoir. FIG. 27 depicts average mortality ofAedes albopictus larvae after 24 hours of exposure to various treatmentsof the end product. Column 160 is 24-hour mortality rate for a controlgroup (water only) while columns 162-176 are 24 hour mortality rates fordoses of end product as listed under the respective column. Columns 160,162, 164 166, 168, 170 and 172 represents the mortality rate when asurfactant was added. Columns 174 and 176 represent the mortality ratewith no surfactant.

As shown in FIG. 27, a dose rate of about 0.28 ml/gal of end product(with copper equivalent of about 4.5 ppm) shows a 24-hour mortality rateof about 80%, shown by column 172. Lower doses (e.g., 0.07 ml/gal (1.2ppm copper)) may result in 24 hour mortality rates of about 10%, asshown by column 170. The dose rates shown in FIG. 27 may, however, notbe suitable for practical use. The data shown in FIG. 27, however, doessuggest that mosquito eradication may be time dependent (e.g., totalcopper uptake dependent) instead of concentration dependent. Thus, insome embodiments, the end product may be provided to a body of water ata relatively low concentration (e.g., at most about 0.25 ppm copperequivalent). The end product may be left in the body of water for anextended period of time to eradicate or disrupt the life cycle ofmosquitoes in the body of water.

In some embodiments, the base product fluid is used to produce an endproduct that potentially could be used as swimming pool sanitizer.Chlorine is the most widely used sanitizer for swimming pools. The onlyEPA recognized sanitizer other than chlorine is a system that usesbiguanides and is sold under the trade name BACQUACIL®(www.bacquacil.com). There are currently no copper based products thathave shown the efficacy to be approved by the EPA for use as a swimmingpool sanitizer. In some embodiments, the end product is dosed into aswimming pool at levels to maintain the copper concentration betweenabout 0.25 ppm and about 1.0 ppm. In some embodiments, the end productis formed from a solid (or powdered) base product mixed with a coppersulfate powder. The solid base product and copper sulfate mix may beformed into a solid shape or delivered using a metered delivery systeminto the swimming pool. The solid base product and copper sulfate mixmay activate (rehydrate) when added to the swimming pool water.

In some embodiments, the base product fluid is used to produce an endproduct that is used as an algaecide. Copper may be used as a primaryactive ingredient against algae. There are certain species of algae,however, that do not respond well to copper alone. For example, blackalgae may not be well controlled with a copper based product alone. Insome embodiments, the end product includes the addition of differentmetals other than copper to target specific algae strains and/or providea broad spectrum product. For example, metals such as, but not limitedto, silver or zinc may be added to the end product in addition to copperor in place of the copper.

In some embodiments, the base product fluid is used to produce an endproduct that is used for micronutrient delivery (e.g., an agriculturetreatment solution used to increase the nutritional value ofagricultural crops). The base product fluid may have improved chelatingproperties including holding the metal or metal salts in solution whilealso providing uptake of the metal or metal salts to plants or crops.Because of these improved properties, the base product fluid may be usedin agriculture treatment solution formulations with compositions similarto those found in the market for traditional chelates such as EDTA. Forexample, one agriculture treatment solution formulation may include anend product that is a 9% zinc solution with the base product fluid. Theformulation may be used as a foliarly applied micronutrient and may beapplied at a rate of approximately one to two quarts per acre to cropssuch as corn, soybeans, and rice. Foliar application methods includemixing with pesticides and spraying it aerially, adding to theirrigation water in traditional pivot irrigators, or applying directlyas a dilute water solution or mixing with pesticides through truckmounted spray units. In some embodiments, the end product includes amixture containing zinc, magnesium, manganese, selenium, molybdenum,boron, iron, cobalt, copper, bismuth, or combinations thereof to supplya broad spectrum micronutrient application. The broad spectrummicronutrient application may be applied to agricultural crops such ascorn and soybeans, which are typically treated with one or more metalscomplexed with EDTA. The end product for micronutrient delivery mayprovide a higher micronutrient uptake than EDTA due to the improvedchelating properties of the base product fluid.

An illustrative example of micronutrient delivery is the delivery ofzinc (Zn) complexed to the chelant detailed herein to growing plants viafoliar application. In this example, the experiment design was aRandomized Complete Design of 4 treatments of 10 replications for eachof five parameters: (1) total chlorophyll by measuring fluorescence, (2)total carotenoids by measuring absorbance following organic solventextraction, (3) electron transport rate by measuring light absorptionand fluorometry, (4) membrane leakage by measuring change in electrolyteconcentrations, and (5) leaf tissue concentrations of zinc by digestingsamples in nitric acid followed by atomic absorption spectrophotometry.Leaf samples were collected at weekly intervals after squaring. Cottonplants (Gossypium hirsutum L.) were grown in a climate controlledchamber on a 14/10 hour, 30/20° C. diurnal cycle, respectively.Individual plants were grown in 48, 3 liter pots containing nutrientdeficient potting soil. Plants received identical treatment fornutrition and growth management until squaring. At squaring, the firstround of measurements were made and treatments sprayed via a CO₂backpack sprayer with plants arranged in rows. Sprays were allowed todry before returning to the climate controlled chamber to minimize crosscontamination of treatments due to foliar contact. Plants were thengrown for an additional two to three weeks with nutrients being suppliedvia zinc-free Hoagland's solution without added Zn for treatments:ESL-Zn (base product fluid solution), Zinc Sulfate, and Low Zinc. Theelemental composition of Hoagland's solution is as follows: N 210 mg/L,K 235 mg/L, Ca 200 mg/L, P 31 mg/L, S 64 mg/L, Mg 48 mg/L, B 0.5 mg/L,Fe 1 to 5 mg/L, Mn 0.5 mg/L, Zn 0.05 mg/L, Cu 0.02 mg/L, and Mo 0.01mg/L. The four treatments and descriptions were (1) “Control” (no foliarspray addition of Zn), (2) “Low Zn” (No foliar spray addition and the Znconcentration of the Hoagland's solution was reduced to 0.025 mg/L, (3)“ZnSO₄” (Foliar spray equivalent of 1% solution [e.g., 8 lbs. of 36%ZnSO₄ in 100 gallons H₂O] at 15 gallons/acre, and (4) “ESL-Zn” (Foliarspray equivalent of 1% solution [e.g., 8 lbs. of 36% ZnSO₄ in 100gallons H₂O] at 15 gallons/acre). Results of the four treatments arepresented in TABLE 5:

TABLE 5 Chlorophylls Carotenoids Electron (μg (μg Transport Rate Znpigments/mg carotenoids/mg (μmol electrons Membrane (ppm or WeekTreatment dry weight) dry weight) m⁻² s⁻) Leakage (%) mg/L) 1 Control13.76 2.181 63 16.39 39.39 ESL-Zn 12.79 1.732 70 35.54 29.00 Low Zn12.17 1.673 61 32.34 27.09 ZnSO₄ 11.88 1.713 71 34.68 27.46 2 Control13.47 2.128 70 21.15 36.56 ESL-Zn 13.71 2.335 82 25.68 88.99 Low Zn10.02 1.567 53 34.79 27.73 ZnSO₄ 12.67 2.322 70 28.12 61.29 3 Control11.58 1.944 68 19.12 28.54 ESL-Zn 12.89 1.807 84 22.01 42.72 Low Zn 7.821.298 55 36.77 21.88 ZnSO₄ 10.72 1.559 68 27.06 27.52

As illustrated in TABLE 5, chlorophylls within leaf tissues treated withzinc supplements increased after application in week one. However, theESL-Zn product maintained greater tissue concentrations into week twocompared to the standard supplement of zinc sulfate. Analysis indicatesthat leaf tissue treated with a zinc supplement was capable ofincreasing their total carotenoid concentrations. Likewise, chlorophyllswithin leaf tissues treated with zinc supplements increased afterapplication in week one. However, the ESL-Zn product maintained greatertissue concentrations into week two compared to the standard supplementof zinc sulfate. The results demonstrate that zinc supplementsstimulated carotenoid production. However, two weeks followingapplication, carotenoid concentrations decreased significantly in thezinc supplemental treatments, though the ESL-Zn product maintained agreater concentration compared to zinc sulfate. Higher values of ETR(electron transport rate) indicate a greater relative rate ofphotosynthesis. Before application in week one, plants were all verysimilar in their values with plants to be treated with zinc sulfatepossessing slightly greater rates. However, following application andinto week two, rates of ETR diverged. ESL-Zn treated plants had thehighest rates compared to the other treatments. Larger amounts ofmembrane leakage indicated as a percent difference, indicate lessenedcapacity for the leaf tissue to maintain membrane structure. Analysisindicates that both zinc sulfate treatment and ESL-Zn treatmentsupplementations decreased membrane leakage percentages. However, leavestreated with ESL-Zn maintained greater leakage control into week two ascompared to the zinc sulfate treatment. Zinc deficiencies in cottontypically occur when leaf tissue concentrations fall below 20 ppm. Onthe day of application, all treatment values were above the deficientlevels. One week after application, both zinc sulfate treatment andESL-Zn treatment increased tissue zinc levels significantly. By week twofollowing applications, the concentrations of Zn in zinc sulfate treatedleaves had decreased but the concentration in ESL-Zn treated leaves wasapproximately two-fold greater than that in other treatments.

In some embodiments, the base product fluid is used to produce an endproduct that is used as an adjuvant to move or be moved (e.g., viacellular membrane transport systems) compounds across cell membranes.For example, a herbicide used with agricultural crops may include thebase product fluid to increase the efficacy of the herbicide. In someembodiments, the end product is to increase the efficiency forfertilization of plants or crops.

In some embodiments, the base product fluid is used to produce an endproduct that is used for potable water treatment. In some embodiments,the base product fluid is used to produce an end product that is used toremove bacteria and/or cyanobacteria from water-based systems. In someembodiments, the end product is used to help pretreat algae, organics,bacteria, and/or cyanobacteria in a water source. New EPA rules aremandating that surface water treatment plants reduce their use ofchlorine in order to reduce disinfection by products. The end productmay provide enhanced anti-microbial properties due to more rapidpenetration through cell walls. Thus, in some embodiments, the endproduct may be used to maintain bacterial control of the water prior togoing into the public distribution system by removing E. coli,cryptosporidium, and giardia at lower concentrations. E. coli and otherbacterial species may exist as cells in the water matrix (e.g.,planktonic cells) or attached to a surface where they may form a complexlayer referred to as a biofilm. When attached to the surface as thebiofilm, bacterial species are typically less susceptible to chlorineand other antimicrobial agents. Due to the chemical nature of the endproduct described herein, it is anticipated that planktonic cells andthose in biofilms may be susceptible to the end product's antimicrobialaction. The use of the end product may reduce chlorine dose rates andassist in compliance with new EPA rules. Additionally, the end productmay improve the economics of treatment compared to current treatmentsusing chlorine.

As shown in TABLES 6 and 7, the end product formed from the base productfluid produced by system 50 shows effective inhibition (e.g., kill) ofE. coli.

TABLE 6 TEST RESULTS FOR End Product formed from Base Product Fluid TestOrganism: Escherichia coli Exposure Time DILUTION 10 minutes 1 hour 2hours 3 hours (VOLUME PLATED) Number of Survivors 10⁰ (1.00 mL) T, T T,T T, T 80, 76 10⁰ (0.100 mL) T, T T, T 126, 100 16, 21 10⁻¹ (0.100 mL)T, T  82, 106 21, 18 3, 1 10⁻² (0.100 mL) 86, 80 13, 18 1, 0 0, 1 10⁻³(0.100 mL) 10, 23 2, 1 0, 0 0, 0 T = Too Numerous To Count (>300colonies)

TABLE 7 CALCULATED DATA FOR End Product formed from Base Product FluidCFU/mL in Test Exposure Population Control CFU/mL of Log₁₀ Percent LoginTest Organism Time Log₁₀ Survivors Survivors Reduction ReductionEscherichia coli 10 minutes 1.75 × 10⁶ 8.3 × 10⁵ 5.92 52.6% 0.32 1 hour(6.24) 9.4 × 10⁴ 4.97 94.6% 1.27 2 hours 1.13 × 10⁴  4.05 99.4% 2.19 3hours 7.8 × 10² 2.89 >99.9% 3.35 CFU = Colony Forming Units

In some embodiments, the base product fluid is used to produce an endproduct that is used as a fungicide. For example, the end product may beused for fungal control on plants in greenhouses, fields, andresidential and commercial locations. In some embodiments, the baseproduct fluid is used to produce an end product that is used fortreatment of water used in shellfish depuration processes and/ortreatment of water used in aquaculture facilities to inhibit odors andto control cyanobacteria (e.g., toxin producers). In some embodiments,the base product fluid is used to produce an end product that is used asan adjuvant to move compounds across cell membranes. In someembodiments, the base product fluid is used to produce an end productthat is used in a cold cream product or other facial or beauty products.For example, the end product may be used for topical treatment of skinwounds, ulcers, or other external infections.

While the above embodiments describe a process for making a base productfluid using sulfuric acid and the uses of the sulfuric acid-based, baseproduct fluid, in some embodiments, other acids may be used instead ofor in combination with sulfuric acid to produce an alternative baseproduct fluid. The alternative base product fluid may have differentstructures and/or different properties depending on the combination ofacids used to make the base product fluid. Examples of acids that may beused include, but are not limited to, phosphoric acid (H₃PO₄),hydrochloric acid (HCl), and nitric acid (HNO₃). Additional acids thatmay be used include, but are not limited to, variations or derivativesof phosphoric acid such as polyphosphoric acid and phosphorous pentoxide(P₂O₅) and/or other hydrogen halides such as hydrofluoric acid fluoride,hydrobromic acid, or hydroiodic acid (in addition to their anhydrides).Acids, especially hydrogen halides, may be provided in either liquid orgaseous form.

In some embodiments, the alternative acid is used in combination withsulfuric acid. For example, the alternative acid may be used as thesecond portion of acid added to the intermediate of the base productfluid instead of sulfuric acid (e.g., the alternative acid is added insubsystem 400, shown in FIG. 1). The second portion of alternative acidmay be added to the intermediate with the intermediate formed bysulfuric acid being in either reaction solution (e.g., fluid form) or insolid form. In embodiments with phosphoric acid added as the secondportion of acid to the intermediate of the base product fluid, theresultant alternative base product fluid may include a mix of sulfuricacid and phosphoric acid ammonium based compounds. In embodiments withhydrochloric acid (or other hydrogen halides) added as the secondportion of acid, the resultant alternative base product fluid mayinclude a mix of sulfuric acid and hydrochloric acid ammonium basedcompounds. In embodiments with nitric acid added as the second portionof acid, the resultant alternative base product fluid may include a mixof sulfuric acid and nitric acid ammonium based compounds.

In some embodiments, the alternative acid is used instead of sulfuricacid throughout process 50, shown in FIG. 1. For example, thealternative acid may be used as the acid reacted with ammonia and waterin subsystem 200 as well as the acid added to the (new) intermediate ofthe base product fluid in subsystem 400. The resultant alternative baseproduct fluid may include a cluster of ammonium salts, the alternativeacid, and water. The ammonium salts may include, for example, one ormore ammonium salts derived from the alternative acid. In embodimentswith phosphoric acid as the acid, the resultant alternative base productfluid may include clusters of ammonium and phosphoric acid basedcompounds. In embodiments with hydrochloric acid (or other hydrogenhalides) as the acid, the resultant alternative base product fluid mayinclude clusters of ammonium and hydrochloric acid based compounds. Inembodiments with nitric acid added as the acid, the resultantalternative base product fluid may include clusters of ammonium andnitric acid based compounds.

Although specific embodiments have been described above, theseembodiments are not intended to limit the scope of the presentdisclosure, even where only a single embodiment is described withrespect to a particular feature. Examples of features provided in thedisclosure are intended to be illustrative rather than restrictiveunless stated otherwise. The above description is intended to cover suchalternatives, modifications, and equivalents as would be apparent to aperson skilled in the art having the benefit of this disclosure.

It is to be understood the invention is not limited to particularsystems described which may, of course, vary. It is also to beunderstood that the terminology used herein is for the purpose ofdescribing particular embodiments only, and is not intended to belimiting. As used in this specification, the singular forms “a”, “an”and “the” include plural referents unless the content clearly indicatesotherwise. Thus, for example, reference to “a valve” includes acombination of two or more valves and reference to “a fluid” includesmixtures of fluids.

Further modifications and alternative embodiments of various aspects ofthe embodiments described in this disclosure will be apparent to thoseskilled in the art in view of this description. Accordingly, thisdescription is to be construed as illustrative only and is for thepurpose of teaching those skilled in the art the general manner ofcarrying out the embodiments. It is to be understood that the forms ofthe embodiments shown and described herein are to be taken as thepresently preferred embodiments. Elements and materials may besubstituted for those illustrated and described herein, parts andprocesses may be reversed, and certain features of the embodiments maybe utilized independently, all as would be apparent to one skilled inthe art after having the benefit of this description. Changes may bemade in the elements described herein without departing from the spiritand scope of the following claims.

What is claimed:
 1. A chelating compound formed by a method comprising:adding anhydrous liquid ammonia and a first portion of an acid to waterand mixing to form a mixed fluid; cooling the mixed fluid to form anintermediate fluid; and adding a second portion of the acid to theintermediate fluid to form a product fluid comprising the chelatingcompound, wherein the second portion of the acid is greater, by weight,than the first portion of the acid, and wherein the acid comprises aphosphoric acid, a derivative of a phosphoric acid, a hydrogen halide ora nitric acid.
 2. The chelating compound of claim 1, wherein thechelating compound comprises a molecular cluster of molecules comprisingone or more ammonium salts, the acid, and water.
 3. The chelatingcompound of claim 1, wherein the method further comprises maintainingthe ammonia as a liquid by cooling the ammonia to a temperature below aboiling point of ammonia at a pressure above atmospheric pressure. 4.The chelating compound of claim 1, wherein the ammonia and acid aremixed in a process line, and wherein the method further comprisesmaintaining a pressure in the process line between about 40 psig andabout 80 psig.
 5. The chelating compound of claim 1, wherein the methodfurther comprises combining the product fluid with a metal salt to forman end product.